Observation of Radical Rebound in a Mononuclear Nonheme Iron Model Complex
Thomas M Pangia, Casey G Davies, Joshua R Prendergast, Jesse B Gordon, Maxime A Siegler, Guy NL Jameson, David P Goldberg
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | AMER CHEMICAL SOC | Published : 2018
A nonheme iron(III) terminal methoxide complex, [FeIII(N3PyO2Ph)(OCH3)]ClO4, was synthesized. Reaction of this complex with the triphenylmethyl radical (Ph3C•) leads to formation of Ph3COCH3 and the one-electron-reduced iron(II) center, as seen by UV-vis, EPR, 1H NMR, and Mössbauer spectroscopy. These results indicate that homolytic Fe-O bond cleavage occurs together with C-O bond formation, providing a direct observation of the "radical rebound" process proposed for both biological and synthetic nonheme iron centers.
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Awarded by NIH
The NIH (GM119374 to D.P.G. and G.N.L.J.) is gratefully acknowledged for financial support. G.N.L.J. further thanks the University of Otago and the Faculty of Science, University of Melbourne, for financial support.